Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C19/00—Alloys based on nickel or cobalt
  • C22C19/03—Alloys based on nickel or cobalt based on nickel
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/20—Conductive material dispersed in non-conductive organic material
  • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/16—Metallic particles coated with a non-metal
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/002—Details
  • H01G4/005—Electrodes
  • H01G4/008—Selection of materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/002—Details
  • H01G4/005—Electrodes
  • H01G4/008—Selection of materials
  • H01G4/0085—Fried electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
  • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
  • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
  • H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
  • H01L23/49883—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials the conductive materials containing organic materials or pastes, e.g. for thick films
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
  • H01F27/00—Details of transformers or inductances, in general
  • H01F27/28—Coils; Windings; Conductive connections
  • H01F27/29—Terminals; Tapping arrangements for signal inductances
  • H01F27/292—Surface mounted devices
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/30—Stacked capacitors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
  • H01L2924/0001—Technical content checked by a classifier
  • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated

Definitions

• the present invention relates to a nickel-based alloy powder used for forming a conductor in the field of electronics.
• the present invention relates to nickel rhenium alloy powder containing nickel as a main component and a conductor paste containing this alloy powder, which is suitable for forming internal electrodes of multilayer ceramic electronic components such as multilayer capacitors, multilayer inductors, and multilayer actuators. .
• Multilayer ceramic electronic components are generally manufactured as follows.
• a ceramic green sheet (hereinafter referred to as “ceramic sheet”) prepared by dispersing ceramic raw material powders such as a dielectric, a magnetic body, and a piezoelectric body in a resin binder and forming a sheet is prepared.
• a conductive paste for internal electrodes in which an inorganic powder containing conductive powder as a main component and optionally containing ceramic powder or the like is dispersed in a vehicle containing a resin binder and a solvent, is printed in a predetermined pattern. And drying to remove the solvent and form a dry film of internal electrodes.
• a plurality of ceramic sheets having the obtained internal electrode dry film are stacked and pressure-bonded to obtain an unfired laminate in which ceramic sheets and internal electrode paste layers are alternately laminated. After cutting this laminate into a predetermined shape, it undergoes a binder removal process in which the binder is thermally decomposed and scattered, and then fired at a high temperature to simultaneously sinter the ceramic layer and form the internal electrode layer. Get the prime body. Thereafter, terminal electrodes are baked on both end faces of the element body to obtain a laminated electronic component. The terminal electrode may be fired at the same time as the unfired laminate.
• the temperature at which the ceramic particles constituting the ceramic sheet begin to sinter is generally much higher than this, and when co-fired with the internal electrode paste containing the nickel powder, the ceramic layer is combined with the nickel film. Therefore, the nickel film is pulled in the surface direction. For this reason, it is considered that the small void force S generated in the nickel film by sintering at a relatively low temperature, and it expands with the progress of sintering in a high temperature region, and tends to become a large hole. If a large air gap is generated in the internal electrode in this way, the resistance value increases or the wire breaks, and the capacitance of the capacitor decreases.
• fine nickel powder since fine nickel powder has high surface activity, when debinding in a non-oxidizing atmosphere such as a nitrogen atmosphere, it acts as a decomposition catalyst for the vehicle, and the resin has a normal decomposition temperature. May explosively decompose at lower temperatures. In this case, cracking caused by a sudden gas generation will not only cause delamination, but the resin will not completely volatilize and carbonaceous residue will be generated. The occurrence of structural defects and reduced reliability are problems. That is, after debinding When the carbon force S remaining on the partial electrode layer is oxidized, gasified and scattered in the subsequent ceramic sintering process at high temperatures, oxygen is extracted from the ceramic layer to reduce the strength of the ceramic body, Or deteriorate electrical characteristics such as insulation resistance. Carbon may also cause oversintering by lowering the melting point of the nickel powder.
• Patent Document 1 discloses that a nickel oxide is reduced during firing by forming a dense oxide film having a certain thickness on the surface of nickel powder. It is disclosed that delamination can be prevented by suppressing changes in volume and weight due to the above, and by increasing the sintering start temperature. However, forming an oxide film on the surface of nickel powder has little effect on suppressing oversintering of 1S Nikkenore, which is effective in preventing structural defects and resistance. In addition, the oxide film present on the nickel powder surface is thought to have the effect of reducing the activity on the nickel surface.
• the particle size is on the order of submicron, especially 0.5 m or less, the activity becomes higher, so that the discontinuity of the electrodes and the deterioration of characteristics due to residual carbon during binder removal are suppressed. I can't.
• Patent Document 2 delamination or the like is performed by optimizing the sintering temperature by using nickel ultrafine powder containing silicon having a specific particle diameter of 0.5 to 5.0% by weight. It describes preventing cracks from occurring.
• Patent Document 3 discloses that the rapid thermal shrinkage start temperature is increased by using composite nickel fine powder in which oxides such as titanium oxide and silicon oxide are present on the surface of nickel powder subjected to surface oxidation treatment. To prevent structural defects such as delamination and cracks. However, this method has not been effective in reducing the thickness of the electrode.
• Patent Document 4 as the conductive powder, including high have ruthenium melting point than nickel as the main component of nickel, rhodium, rhenium, at least one element of the platinum 20 mole 0/0 or less, the average particle size 0.01 to 1.0;
• ruthenium melting point than nickel as the main component of nickel, rhodium, rhenium, at least one element of the platinum 20 mole 0/0 or less, the average particle size 0.01 to 1.0;
• Patent Document 5 there are few ruthenium, rhodium, rhenium and platinum on the surface of nickel powder. It is described that a conductive paste using a powder having a coating layer containing at least one element has the same effect!
• Patent Document 1 Japanese Unexamined Patent Publication No. 2000-45001
• Patent Document 2 Japanese Patent Laid-Open No. 11 189802
• Patent Document 3 Japanese Patent Laid-Open No. 11 343501
• Patent document 4 WO2004 / 070748
• Patent Document 5 Japanese Patent Application Laid-Open No. 2004-319435
• Nikkenorelenium alloy powders are excellent materials capable of forming a thin internal electrode layer without adversely affecting the characteristics of the dielectric.
• nickel rhenium alloy powder tends to be more active than pure nickel powder, and especially when the particle size is extremely small, the sintering progresses at a low temperature when the conductor paste is fired. May cause degradation.
• an internal electrode of a multilayer ceramic electronic component such as a multilayer ceramic capacitor is formed using the low activity even though it is extremely fine, the ceramic layer and the sintering shrinkage behavior are further improved.
• a rhenium or nickel alloy powder that can be approximated and can prevent oversintering at high temperatures, and therefore can form a thinner and more continuous internal electrode, and a conductor paste using the same.
• the purpose is to do.
• Renium Mu nickel alloy that can produce highly laminated, compact, and highly reliable multilayer ceramic electronic components that do not deteriorate in electrical characteristics such as capacitance even when the internal electrodes are made thinner and have no structural defects.
• An object of the present invention is to provide a powder and a conductive paste for an internal electrode of a multilayer ceramic electronic component using the powder.
• the present invention has the following configuration.
• a nickel-rhenium alloy powder characterized by containing nickel as a main component, 0 ⁇ ;! to 10% by weight of rhenium, and 50 to 10 ppm of silicon in terms of silicon atoms.
• a conductor paste for forming an internal electrode of a multilayer ceramic electronic component comprising the nickel rhenium alloy powder according to any one of (1) to (6) as a conductive powder.
• the silicon-containing nickel rhenium alloy powder of the present invention is used to form an internal electrode of a multilayer ceramic electronic component, even if it is a very fine powder, the start and progress of sintering during the firing are delayed. The sintering shrinkage behavior between the electrode layer and the ceramic layer can be approximated. Moreover, the electrode is not spheroidized by oversintering. Therefore, a thin, low void electrode with low resistance is formed. For this reason, for example, in the case of a multilayer ceramic capacitor, the internal electrode layer and the ceramic layer that do not cause a decrease in electrical characteristics such as a decrease in electrostatic capacity can be made thinner, and a reduction in size and an increase in the number of layers can be achieved. . In addition, a highly reliable multilayer ceramic electronic component can be obtained with a high yield even in a highly laminated product having a thin ceramic layer and internal electrode layer with few structural defects such as delamination and cracks.
• the rhenium content in the nickel rhenium alloy powder is in the range of 0.01 to 10% by weight with respect to the total amount of the alloy powder.
• the content is less than 0.01% by weight, for example, when used as an internal electrode of a multilayer ceramic electronic component, the effect of suppressing the oversintering of nickel becomes small, and it becomes difficult to make the internal electrode thin.
• rhenium exceeds 10% by weight, the phase of the rhenium phase or the rhenium-rich phase may precipitate due to the difficulty of forming a homogeneous alloy, and the properties as a nickel rhenium alloy will be impaired.
• rhenium is hundreds when oxidized.
• the alloy composition changes due to oxidation during firing, or from the internal electrode part of the formed laminated part
• Sublimated rhenium oxide may adversely affect the dielectric.
• the rhenium content is particularly preferably in the range of 1.0 to 8.0% by weight.
• the alloy composition of the individual alloy particles constituting the nickel rhenium alloy powder does not necessarily have to be uniform, for example, alloy particles having a rhenium concentration gradient from the particle surface to the center may be used! / ,.
• nickel rhenium alloy powder contains nickel and rhenium as main components and other components other than silicon! /.
• Other components include platinum, palladium, iron, cobalt, ruthenium, rhodium, etc. that can be alloyed with rhenium, and in small amounts, gold, silver, copper, tungsten, niobium, molybdenum, vanadium, chromium, Metal elements such as zirconium and tantalum may be contained. Further, it may contain a small amount of light elements that can reduce the catalytic ability of nickel, such as sulfur and phosphorus.
• the nickel rhenium alloy powder of the present invention preferably has an average particle size in the range of about 0.05 to 1.0 m. If less than 0.05 in, the activity is too high and low temperature sintering or low It becomes difficult to suppress the decomposition of the resin at the temperature. In addition, when a conductor paste is manufactured, a large amount of organic components such as a solvent and a dispersant are required to disperse and obtain appropriate viscosity characteristics. A film cannot be obtained, and therefore, a fired film having good continuity is formed. In order to reduce the thickness of the internal electrode layer in response to the demand for miniaturization and high lamination of multilayer electronic components, the average particle diameter of the nickel rhenium alloy powder is preferably 1.0 m or less.
• the average particle size is 0.05-0. ⁇ ⁇ ⁇ ⁇
• the specific surface area is 1.5 to 15 m 2 / g. It is preferable to use a powder having good dispersibility.
• the average particle diameter of the powder represents the specific surface area diameter converted from the specific surface area measured by the BET method unless otherwise specified.
• the silicon component may be dissolved or dispersed in the nickel rhenium alloy powder, but it is desirable that at least a part of the silicon component exists in the vicinity of the surface of the alloy powder. In the case where an oxide film is formed, it is desirable that the oxide film be present in the surface oxide film.
• Silicon is considered to decrease the activity of the nickel rhenium alloy and adjust the sinterability, thereby forming an extremely thin and highly continuous internal electrode film. Since silicon is present in the vicinity of the particle surface, it acts more effectively, and can also stabilize the binder decomposition behavior in the binder removal process of the conductor paste.
• silicon oxide is combined with the nickel oxide or rhenium oxide to stabilize the oxide film. It is conceivable that. As a result, a close oxide film is reliably maintained on the surface of the nickel-rheum alloy powder to a certain high temperature during firing, and as a result, the sintering start temperature rises and the progress of oxidation during firing is suppressed. It is preferable because it can form an excellent internal electrode film that is thinner and has less voids, and has fewer structural defects such as delamination and a laminated electronic component.
• silicon has a function of forming a uniform surface oxide film on the nickel rhenium alloy powder as described later, and the silicon powder contains a silicon component when the surface of the nickel rhenium alloy powder is oxidized.
• the entire alloy particle surface is thin and uniform An oxide film coated on the substrate is reliably formed. For this reason, it is considered that the effect of suppressing the sintering of the powder and the effect of improving the oxidation resistance become more remarkable.
• the content of silicon is 50 to 10 ppm in terms of silicon atoms with respect to the total weight of the powder. If it is less than 50 ppm, the effect of improving the continuity of the internal electrode is insufficient 10, and if it is more than OOOppm, the influence on the dielectric properties cannot be ignored, and excessive silicon is thought to inhibit the densification of the film. , Electrode continuity is reduced. In order to obtain a thin internal electrode with few voids, the range of 100 to 5, OOOppm is preferable.
• the nickel rhenium alloy powder of the present invention preferably has a thin oxide film formed on the surface. Since such a surface oxide film reduces the activity of the nickel rhenium alloy powder, when this nickel rhenium alloy powder is used to form the internal electrode of the multilayer ceramic electronic component, the multilayer ceramic electronic component is fired. Further, by further delaying the progress of sintering shrinkage in the low temperature region of the internal electrode layer, it is possible to stably form an internal electrode film that is thinner and has less voids and has high continuity. Further, since further oxidation during firing is suppressed, oxidation resistance is excellent, and delamination and cracks due to volume change due to oxidation-reduction during firing are prevented.
• the average thickness is as thin as about 30 nm or less, and / or the entire surface is covered with a stable oxide film!
• the above effect is preferable.
• the amount of the surface oxide film is a ratio of the total oxygen amount contained in the surface oxide film to the whole alloy powder, and is preferably about 0.;! To 3.0% by weight. If the amount of oxygen is less than 0.1% by weight, the thickness of the oxide film becomes thin and the entire surface cannot be covered, so the effect of surface oxidation becomes small. On the other hand, if it exceeds 3.0% by weight, gas generation and volume change due to reduction of the oxide increase when the laminated electronic component is baked in a reducing atmosphere, making it difficult to obtain a dense electrode film. Cracks can cause delamination.
• the oxygen amount of the surface oxide film of the alloy powder is N gas containing 4% of H.
• the nickel rhenium alloy powder preferably contains a sulfur component. It is desirable that sulfur be segregated near the surface of the alloy particles.
• the surface activity of nickel rhenium alloy powder is higher than that of pure nickel. The ability to reduce the surface activity by including silicon and by not exposing the pure metal surface by oxidizing the surface. Can be reduced. This prevents the resin from abruptly decomposing at low temperatures due to catalysis during binder removal, resulting in structural defects and carbon residue, resulting in a decrease in element strength and electrical performance. Is
• This action is due to the presence of sulfur in the vicinity of the surface of the alloy powder particles, particularly in the case where a surface oxide film is present, where the oxide film is partially thin. This is thought to be because the surface oxide film is not desorbed from the surface even when the surface oxide film is reduced in a strong reducing atmosphere at the time of binder removal, where the binding strength to nickel is strong.
• the content of sulfur is preferably 100 to 2,0OOppm in terms of sulfur atoms with respect to the weight of the whole powder. If the amount is less than OOppm, the effect of decreasing the surface activity is weak. If the amount is more than 2, OOOppm, there is a concern about the influence on the dielectric characteristics, and damage to the firing furnace by sulfur-containing gas generated during firing of multilayer ceramic electronic components. Can no longer be ignored
• JP-A-2007-138280 is compositionally homogeneous and fine.
• the nickel rhenium alloy powder is preferable because it can be produced easily and stably.
• the main component metal particles such as nickel in a solid phase and / or a liquid phase are dispersed in the gas phase, and the rhenium oxide vapor is reduced to reduce the metal. Rhenium is deposited on the surface of the particles and diffuses into the particles at high temperatures.
• the method of incorporating silicon into the nickel rhenium alloy powder is not particularly limited.
• a nickel rhenium alloy powder is produced by the method described above, a silicon-containing nickel rhenium alloy powder is produced by containing silicon or a silicon compound in the raw material, and at the time of producing the nickel rhenium alloy powder, A method of producing a silicon-containing nickel-rheum alloy powder by containing a silicon compound gas or volatile silicon compound vapor in the manufacturing atmosphere, and a nickel rhenium alloy powder dispersed in a solution containing a silicon compound or a silicon oxide colloid And a method of producing a silicon-containing nickel rhenium alloy powder by heat treatment.
• JP-A-2007-138280 there is a method in which silicon is previously contained in nickel powder as a raw material, a silane compound or a siloxane compound together with rhenium oxide vapor.
• a method of feeding any silicon compound as a gas is preferably employed.
• the method of forming the surface oxide film on the nickel rhenium alloy powder of the present invention is not limited, for example, the surface of the alloy powder is oxidized by heating in an oxidizing atmosphere while preventing aggregation. Can be made. Further, for example, in the vapor deposition method, the method of thermally decomposing a thermally decomposable metal compound powder described in JP-A No. 2002-20809 or the method described in JP 2007-138280, a high temperature In the process of cooling while the alloy powder produced in step 1 is dispersed in the gas phase, by mixing an oxidizing gas such as air, a uniform, thin layer and oxide film can be formed instantaneously without causing agglomeration of the powder. This is preferable. In this case, the force S is used to adjust the oxidation amount according to the temperature at which the generated particles come into contact with the oxidizing gas.
• the nickel rhenium alloy powder is subjected to surface oxidation, contacted with a silicon compound, and then heat-treated, or silicon-containing nickel rhenium obtained by the above various methods.
• a method in which at least a part of silicon is incorporated into the surface oxide film as an oxide by subjecting the alloy powder to surface oxidation treatment.
• the alloy powder generated at a high temperature as described above is surface-oxidized with an oxidizing gas while being dispersed in the gas phase, the silicon component is preliminarily contained in the alloy powder, so that the silicon component is extracted from the nickel rhenium alloy powder.
• silicon has the effect of uniformly forming a surface oxide film on the nickel rhenium alloy powder, and is preferable because it forms a thin oxide film that uniformly covers the entire alloy particle surface.
• the method of incorporating sulfur into the nickel rhenium alloy powder there is no limitation on the method of incorporating sulfur into the nickel rhenium alloy powder.
• a method in which alloy powder and sulfur powder are mixed and heated in a sealed container and a method in which a gas containing sulfur such as hydrogen sulfide gas or sulfurous acid gas is circulated and reacted in the alloy powder. is there.
• the method of thermally decomposing the metal compound powder described in JP-A No. 2002-20809 or the like, or the method described in JP-A No. 2007-138280 the alloy raw material contains a sulfur compound.
• sulfur-containing nickel rhenium powder can be obtained by adding hydrogen sulfide gas, sulfurous acid gas, mercaptan-based organic sulfur compound gas, etc. to the reaction system.
• the conductor paste of the present invention contains at least the nickel rhenium alloy powder as a conductive powder and is dispersed in a vehicle containing a resin binder and a solvent.
• the resin binder those usually used for conductive pastes that are not particularly limited, for example, senenorose-type lunar essence such as ethenoresenorelose and hydroxyethinoresenorelose, Resin, methacrylic resin, petital resin, epoxy resin, phenol resin, rosin, etc. are used.
• the blending amount of the resin binder is not particularly limited, but is usually about! To 15 parts by weight with respect to 100 parts by weight of the conductive powder.
• the solvent is not particularly limited as long as it dissolves the binder resin, and a solvent usually used in a conductor paste is appropriately selected and blended. Examples thereof include organic solvents such as alcohols, ketones, ethers, esters and hydrocarbons, water, and mixed solvents thereof.
• the amount of the solvent is appropriately determined according to the properties of the conductive powder, the type of resin, the coating method, etc., as long as it is a commonly used amount. Usually 40 to about 150 parts by weight with respect to 100 parts by weight of the conductive powder.
• ceramics containing components that are usually blended that is, ceramics that contain the same or similar composition as the ceramic contained in the ceramic sheet, Glass, alumina, silica, zirconium oxide, metal oxides such as copper oxide, manganese oxide, and titanium oxide, inorganic powders such as montmorillonite, metal organic compounds, plasticizers, dispersants, surfactants, etc., depending on the purpose. Can be blended.
• the conductor paste of the present invention is not limited to a power paste produced by kneading a nickel rhenium alloy powder together with other additive-caro ingredients together with a vehicle and uniformly dispersing according to a conventional method. It may be in ink form.
• the obtained conductor paste is particularly suitable for forming internal electrodes of multilayer ceramic electronic components such as multilayer capacitors, multilayer inductors, multilayer actuators, etc. For forming terminal electrodes of ceramic electronic components and other thick film conductor circuits. It can also be used.
• Nickel acetate tetrahydrate powder was fed to an airflow crusher at a feed rate of 2000 g / hr.
• rhenium oxide (Re 2 O 3) is heated to 300 ° C to generate rhenium oxide vapor.
• the produced powder has a good dispersibility with a uniform particle size composed of spherical particles having an average particle size of about 0.3 am or less.
• the powder was confirmed to be powder.
• STEM scanning transmission electron microscope
• an oxide film was formed on the particle surface.
• ESA photoelectron spectroscopy
• the specific surface area, average particle size, rhenium content, silicon content, oxygen content, sulfur content, and carbon content of the obtained powder were examined and shown in Table 1.
• the specific surface area is measured by the BET method, and the average particle diameter is the converted particle diameter from the specific surface area.
• the rhenium and silicon contents were quantified by inductively coupled plasma spectroscopy (ICP). About 2g of powder was weighed into an alumina boat and the oxygen content was increased from room temperature to 900 ° C in N gas containing 4% H.
• the weight change rate (%) (loss on ignition) when cooled to room temperature after heating was measured, and the value was obtained by subtracting the carbon and sulfur contents from this.
• the sulfur and carbon contents were measured with a carbon / sulfur analyzer (EMIA-320V, manufactured by Horiba, Ltd.). In this example, sulfur is not actively added, so it is considered as an impurity from raw materials and processes.
• the sintering 'shrinkage behavior of the powder was examined as follows. A circle with a diameter of 5mm and a height of about 3mm Using powder molded in a columnar shape as a sample, in N gas containing 4% of H at a rate of 5 ° C / min
• TMA thermomechanical analysis
• Evaluation of the binder removal property of the conductor paste was performed as follows. 100 parts by weight of the obtained alloy powder, 5 parts by weight of ethyl cellulose as a resin binder, and 95 parts by weight of dihydrotitaneol as a solvent were blended and kneaded using a three-roll mill to produce a conductor paste. The obtained conductor paste was applied on a PET film to a thickness of 250 m, and dried at 150 ° C. to remove the solvent. The dried product was heated to 500 ° C at a rate of 20 ° C per minute in a nitrogen gas atmosphere, and thermogravimetric measurement was conducted to determine the decomposition start temperature of the resin. Indicated.
• the continuity of the fired film was measured as follows. 100 parts by weight of the obtained alloy powder, 20 parts by weight of 50 nm barium titanate powder, 5 parts by weight of ethyl cellulose, and 95 parts by weight of dihydrotabineol were blended and kneaded using a three-roll mill to obtain a conductor paste. Produced. The obtained conductor paste was applied onto an alumina substrate so that the amount applied was 0.8 mg / cm 3 in terms of metal, and fired at 1200 ° C in N gas containing 4% of H.
• the fired film was observed by SEM, and the substrate coverage of the fired film was measured by image processing of the observed image. The larger the number, the better the continuity.
• Nickel-Rhenium alloy powder under the same conditions as in Examples 1 to 5 except that hydrogen sulfide gas diluted with nitrogen gas is supplied in addition to rhenium oxide vapor and tetraethoxysilane vapor in an air stream in which nickel acetate powder is dispersed. Manufactured.
• the obtained powder was analyzed, and in the case of V or deviation, it was confirmed that the alloy powder had a spherical oxide powder with a surface oxide film and a uniform particle size and good dispersibility. Also, ESCA confirmed that the surface oxide film contained nickel oxide, rhenium oxide and silicon oxide! /, And that sulfur was present near the particle surface.
• a nickel rhenium alloy powder was produced in the same manner as in Examples 6 to 10 except that the surface oxidation was not performed.
• the obtained powder was a spherical alloy powder with uniform particle size and good dispersibility that was hardly oxidized, and that silicon and sulfur were present near the particle surface. Shinobi.
• Alloy powders having different rhenium contents were produced under the same conditions as in Examples 6 to 10 except that the supply amount of the rhenium oxide vapor was changed.
• Example 15 Under the same conditions as in Examples 6 to 10 except that the supply rate of nickel acetate tetrahydrate powder was 200 g / hr and the supply rate of rhenium oxide vapor was about 3 g / hr in terms of rhenium metal, A rhenium alloy powder was produced.
• a nickel rhenium alloy powder was produced under the same conditions as in Examples 1 to 5 except that tetraethoxysilane was not supplied. However, Comparative Example 2 did not perform surface oxidation treatment.
• Nickel rhenium alloy powders were produced under the same conditions as in Examples 1 to 5 except that the amount of tetraethoxysilane solution was adjusted and the silicon amount was as shown in Table 1.
• a silicon-containing nickel powder containing nickel oxide and silicon oxide on the surface oxide film was produced under the same conditions as in Examples;! To 5 except that rhenium oxide vapor was not supplied.
• Comparative Example To 5 powder specific surface area, average particle size, rhenium content, silicon content, oxygen content, sulfur content, carbon content, TMA shrinkage temperature, removal of conductor paste The binder temperature and the substrate coverage of the fired film were measured in the same manner as in Examples 1 to 5, and are shown in Table 1. The trace amounts of silicon detected in Comparative Examples 1 to 3 and the trace amounts of sulfur detected in Comparative Examples;! To 5 are considered to be impurities derived from raw materials and processes.
• the binder removal temperature is improved by the addition of sulfur, and the effect of suppressing the catalytic activity by sulfur is shown. Further, it is shown that by containing silicon and sulfur at the same time, the binder removal activity can be suppressed and the fired film coverage can be improved without excessive amounts of each.

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• 2007
  • 2007-09-25 MY MYPI20090910 patent/MY152865A/en unknown
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